D

Journal of Materials Science and Engineering A 3 (9) (2013) 615-620

DAVID

PUBLISHING

Structural and Relaxor Behavior of Pb0.95 (La1-xBix)0.05

[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 Ceramics
Hayet Menasra1, Zelikha Necira1 and Ahmed Boutarfaia1, 2
1. Applied Chemistry Laboratory, Exact and Natural and Life Sciences Faculty Materials Science Department, Mohamed Kheider
University of Biskra BP145 7000, Algeria
2. Exact and Natural and Life Sciences Faculty Materials Science Department, University of Ouargla, Ouargla 35000, Algeria
Received: June 05, 2013 / Accepted: July 19, 2013 / Published: September 10, 2013.
Abstract: Polycrystalline samples of Pb0.95(La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 were prepared by high-temperature
solid-state reaction technique. Preliminary X-ray study at room temperature shows the formation of single phase compounds in the
tetragonal crystal system. Scanning electron microscopy (SEM) study was employed to observe the microstructure and distributions of
grains of the sintered ceramics at 1,180 C. Detailed studies of dielectric constant () and tangent loss (tan), of the compounds as a
function of temperature at 1 kHz show that the compounds have a diffuse ferroelectric phase transition. As we increase Bi addition,
Transition temperature shifts towards higher temperature side. Diffusivity () study of phase transition of these compounds provided its
value from 1.59 to 1.78 indicating the degree of the disordering in the system.
Key words: PLZT ceramics, grain size, dielectric properties, diffusivity.

Nomenclature
C:
:
:

Temperature
Diffusivity
Dielectric constant

1. Introduction
Lead zirconate titanate [Pb (Zr, Ti)]O3 (or PZT) are
important ferroelectric materials for a variety of
applications in various piezoelectric, ultrasonics and
sensors in different fields of technology [1-4].
Lanthanum is a donor dopant in PZT with La3+
substitution on Pb2+ sites giving rise to defects of the
type LaPb, where the dot indicates a single positive
excess charge and the subscript indicates the site that
the substitution ion occupies. Each two positive La
charges are compensated by a Pb site vacancy VPb,
where the two primes indicate two negative charges
Corresponding author: Hayet Menasra, Ph.D., research
fields:
ceramics
and
glass
materials.
E-mail:
hayetmenasra@yahoo.com.

associated with the vacancy [5]. This maintains charge

neutrality in the crystal. The effect of addition of rare
earth oxides in PZT ceramics have mostly been related
with the incorporation of La3+ ions into [Pb(Zr, Ti)]O3
ceramics wish increases their dielectric constant,
dielectric loss and decreases mechanical quality
factor [6, 7]. Recently, the influence of soft doping
(trivalent Bi [8-14]) and hard doping (acceptors Mn
and Sb [15-17]) in the perovskite family
[PbLa(Zr,Ti)]O3 have been reported to have a diffuse
phase transition characteristics and/or relaxor
properties. However, the relationship between
morphological and electrical properties with reference
to these combinatorial ceramic compositions with hard
(acceptor Mn and Sb B-site) and soft (trivalent Bi
A-site) doping in PLZT has not been addressed.
In present work, the structural and electrical properties
of ferroelectric ceramics with a general formula:
Pb0.95(La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3; x
= 0, 0.02, 0.04 and 0.06 are studied which were

Structural and Relaxor Behavior of Pb0.95 (La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 Ceramics

3. Results and Discussion

XRD patterns of the PLBZMST perovskite
ceramics sintered at 1,180 C are shown in Fig. 1. The
PZT phase could be identified from X-ray peaks in a
range of 2 ~ 42-47 [20], wish corresponded To
(200)T-(002)T peaks of tetragonal (T) structure. The
associated changes in lattice parameter and degree of
tetragonality (c/a) were listed in Table 1 (Fig. 2a and
2b). The calculated tetragonality of all the samples
indicates that the addition of Bi to PLZMST does not
cause mush variation in tetragonality, except that a
pyrochlore peak is observed near the perovskite (110)
for all the compositions. The relative amount of the
pyrochlore phase to the perovskite phase was
esteemed using the following peak area ration
equation [21].
.

100%

(1)

(211)

(112)

(002)
(200)

(111)

(110)

(101)

pyrochlore

The ceramic samples were prepared by solid state

reaction. High purity raw materials (Pb3O4, ZrO2, TiO2,
La2O3, Bi2O3, MnO2 and Sb2O3) were stoichiometrically
weighed
according
to
the
composition
Pb0.95(La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 via
the chemical route for x = 0.0, 0.2, 0.4 and 0.6. From
now on, we shall refer to this compound as PLBZMST
or 100/0, 80/20, 60/40 and 40/60 according to the La
and Bi ratio. The batch powders were dispersed in
acetone and mixed by a magnetic stirrer during two
hours. The obtained paste is being dried at 80C, and
then crushed in a mortar out of a glass during 4 hours.
Powders were calcined at 900 C for 120 min with a
heating rate of 2 C/min. calcined powders were
crushed in a similar manner to the first crushing but
with 6 h, for better agglomerate size reduction. A 5%
polyvinyl alcohol (PVA) water solution was used as
binder to increase the plasticity of the powders. The
weight ratio between the PVA solution and the
powders was 1:20. Powder and PVA solutions were
mixed in a mortar and then uniaxially pressed into
pellets with a pressure of 2,000 kg/cm3 in a cylindrical
stainless steel dies using a hydraulic press. The size of
those pellets was 13 mm in diameter; while the
thickness is 1 mm. Pellets were packed into covered
alumina crucibles. The inner space of the crucibles was
filled up with the powders of PbZrO3, in order to
prevent intensive evaporation of the lead during the
sintering. A typical sintering schedule consisted of
heating rate of 2 C/ min to 1,180 C, for 120 min and
natural cooling in the furnace.
Powder X-ray diffraction was recorded by X-ray
powder (BRUKER-AXE, D8) diffractometer using
CuK radiation ( = 1,5406 ) in a wide range of
Bragg angles (20 2 60) at a scanning rate of

(100)

2. Experiments

2/min. Densities of sintered pieces were calculated

from the sample dimensions and weights.
Microstructural features such as a grain size and pores
were characterized by means of scanning electron
microscopy (SEM: JEOL JSM-6390LV). Sintered
pellets were electrified by silver paste, and fired at
750 C for forty 5 min, before using for any electrical
measurements. The dielectric permittivity and loss
tangent of the samples were measured as a function of
frequency at different temperature (room temperature
to 500 C) using LCR meter (Good Will Instrument co,
LTD).

(001)

prepared through a high temperature solid-state

reaction technique by satisfying the following
conditions: charge neutrality Goldschmidts tolerance
factor [18, 19].

Intensity (a. u)

616

(La / Bi)
40/60

60/40

80/20

100/0
20

30

40

50

60

2theta(deg.)

Fig. 1

XRD patterns of PLBZMST sintered at 1,180 C.

Structural and Relaxor Behavior of Pb0.95 (La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 Ceramics

617

90
88

relative density
c/a

1.050

86
1.045

Tetragonality (c/a)

Relative density (%)

84
82

1.040

80

1.035

78
76

1.030

74
1.025

72
70

1.020
0.00

0.01

0.02

0.03

0.04

0.05

0.06

Concentration (%)

(a)
(b)
Fig. 2 (a) Plots of relative density and tetragonality vs concentration (mol%) and (b) variation of lattice parameter with
concentration (mol%) of different compositions.

where A pyro. an A(110) are the area under the

pyrochlore peak and the (110) perovskite phase. The
pyrochlore value is increased from 3% to 6% with
increasing Bi doping, which is small and agreement
with the value reported in doped PZT [22]. Hence, this
composition can also be considered as a single phase
wish confirms the homogeneous diffusivity of Bi3+ in
PLZMST perovskite. The donors ions Bi3+ partially
substitute Pb+2 at A-site and acceptors Mn4+ and Sb3+
partially substitutes Zr4+/Ti4+ at B-site due to the
approximately close and similar ionic radii of
respective cations at A-site and B-site in PLZT
lattice.
SEM micrographs of the pellet prepared from
PLBZMST powder and sintered at 1,180 C are shown
in Fig. 3. The sintered pellets have been found to have a
grain size of the order of ~ 2.28 m and uniform grain
distribution, which is in accordance with the high

density value as can be seen from Table1. The

average grain size was determined directly from the
SEM micrographs by using the classical linear
interception method.
Fig. 4a shows the variation of the dielectric constant
(r) as a function of temperature at frequency of 1 kHz.
It is observed that r increases with the increase of
temperature up to the onset of phase transition. A
significant improvement in values of r has been
observed with the increase of sintering temperatures.
The value of dielectric constant (max= 21,728.37) of
the sample doped with Bi (60/40) at a transition
temperature (Tc = 360 C) is a high as 2 times that of
the other samples. On the other hand, while at room
temperature; permittivity increased with dopants
concentration mainly because of the lower values of
porosity. This fact can be explained by using the
Bruggeman model for inhomogeneous media [23].

Fig. 3 SEM micrographs of PLBZMST pellets (a) 100/0; (b) 80/20; (c) 60/40 and (d) 40/60 sintered at 1,180 C.

618

Structural and Relaxor Behavior of Pb0.95 (La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 Ceramics

(a)
(b)
Fig. 4 Variation of (a) Dielectric constant and (b) dielectric loss respectively with temperature at 1 kHz for all samples
sintered at 1,180 C.

Fig. 4b shows the variety of dielectric loss (tan) as a

function of temperature at 1 kHz; for all the
compositions, as temperature increase, loss tangent is
almost constant up to 300 C, but then it starts
increasing with temperature. This increase in (tan)
may be due to an increase in the electrical
conduction of the residual current and absorption
current [24].
It is known that the dielectric constant of a normal
ferroelectric, above the curie temperature follows the
Curie- Weiss Law [25] described by:

Fig. 5
1 kHz.

(2)

where, T0 is the Curie-Weiss temperature and C is the

Curie-Weiss constant. Fig. 5a shows the plot of
temperature versus inverse dielectric constant (at 1 kHz)
fitted to the Curie-Weiss law for PLZMST ceramics.

(3)
The parameter Tm, to illustrate the degree of
deviation from the Curie-Weiss law, was defined as
where Tcw denotes the temperature from which the
permittivity starts to deviate from the Curie-Weiss

(a)
(b)
(a) The inverse as a function of temperature at 1 kHz for PLBZMST, (b) ln(1/ 1/m) vs ln(T Tc) of PLZMST at

619

Structural and Relaxor Behavior of Pb0.95 (La1-xBix)0.05[(Zr0.6Ti0.4)0.95(Mn1/3Sb2/3)0.05]O3 Ceramics

Table 1 The lattice parameters, physical parameters, Theoretical and relative density of PLBZMST at 1,180 C.
A=b

System (tetragonal)
c
c/a
V (3)

3.9615

4.0725

1.02802 63.91

8.5700

71.1

13,059.73

350

28

1.59

3.9936

4.1937

1.05011 66.88

8.5884

79.36

13,275.19

360

26

1.63

3.8928

4.068

1.04501 61.55

8.6193

87.74

21,728.37

360

19

1.78

3.9666

4.0619

1.02403 63.90

8.6251

81.51

28,272.79

410

42

1.73

x%

Theoretical
Relative density
density (gm/cm3)
m

Physical parameters
TC (C)
Tm (C)

law, and Tm represents the temperature of the

dielectric constant maximum. At 1 kHz, it can be seen
from Table 1 that the Tm decreases slightly with
increased Bi addition.
The

dielectrics

characteristics

of

relaxor

ferroelectrics are known to deviate from the typical

Curie-Weiss behavior and can be described by a
modified Curie-Weiss relation-ship [26] where and C
are assumed to be constant.
1

(4)

The parameter give information on the character of

the phase transition: For = 1, a normal Curie- Weiss
law is obtained, = 2 describe a complete diffuse phase
transition [27]. Fig. 5b shows the plot of ln((1/)
(1/m)) versus ln(T-Tm) at 1kHz of PLZMST sample.
Linear relationships were observed. The slopes of the
fitting curve were used to determine the parameter .
The values of are listed in Table 1. It can be seen the
increase in value of with Bi2O3 content (Table 1)
indicates an increase in diffusivity.

4. Conclusions
PLBZMST ceramics, using high temperatures solidstate reaction technique exhibit good homogeneity and
formation of single- phase compounds with tetragonal
structure. Grain size was obtained in the order of ~ 2.28
m and uniform grain distribution wish is in
accordance with the density. The increase in transition
temperature and dielectric constant can be attributed to
the emerging lead vacancies creation by donor cations
(La3+and Bi3+), and acceptor cations (Mn4 +and Sb3+) to
reduce the oxygen vacancies mobility to balance
charge in the modified PLZT. The diffusivity () study

of phase transition of these compounds gives the values

from 1.59 to 1.78 indicating the degree of the
disordering in the system.

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